1. Field of the Invention
This invention relates to new esterification catalysts and esterification processes for crosslinking cellulose as a means of imparting wrinkle resistance and smooth drying properties to cellulosic textiles without the use of formaldehyde or derivatives that release formaldehyde.
2. Description of the Prior Art
There are numerous commercial processes for imparting wrinkle resistance, shrinkage resistance and smooth drying properties to cotton fabrics and garments, so that they retain their dimensions, smooth appearance and normal shape while in use and also when machine washed and tumble dried. In most of these processes, formaldehyde or an addition product of formaldehyde is applied to the cotton textile together with an acid catalyst, and heat is then applied to produce crosslinking of the cotton cellulose molecules.
The crosslinks thus formed in the cellulose impart to the fabric a tendency to return to its original shape and smoothness when deformed by mechanical forces temporarily exerted on the fabric during its use or during laundering and tumble drying.
Formaldehyde addition products with urea, cyclic ureas, carbamate esters or with other amides are widely used crosslinking agents for durable press finishing, as the above wrinkle resistant, smooth drying treatments are called. The formaldehyde addition products, also known as N-methylol agents or N-methylolamides, are effective and inexpensive, but have serious disadvantages. They continuously release vapors of formaldehyde during durable press finishing of cotton fabric, subsequent storage of the treated fabric, manufacture of the resulting garment, retailing of the garment, and finally during use of the garment or textile by the consumer. The irritating effect of formaldehyde vapor on the eyes and skin is a marked disadvantage of such finishes, but more serious is the knowledge that formaldehyde is a carcinogen to animals and apparently also to humans continuously exposed to formaldehyde vapor for very long periods. A need is evident for durable press finishing agents and processes that do not require formaldehyde or its unstable derivatives.
Another disadvantage of the use of N-methylol agents in durable press treatments is that Lewis acid catalysts and high temperatures are required to bring about sufficiently rapid crosslinking of the cotton cellulose by such finishing agents. The Lewis acid catalysts cause undesirable losses of breaking and tearing strength in cotton fabric during the heat curing step. The strength losses are due to degradation of cellulose molecules by the Lewis acid catalysts at elevated temperature. Such strength losses occur over and above the adverse effects on strength of the crosslinkages produced in the cellulose. An added disadvantage of certain nitrogenous finishes is their tendency to retain chlorine from chlorine bleaches, with resultant fabric discoloration and strength loss if subsequently given a touch-up ironing.
The use of polycarboxylic acids with or without catalysts in pad, dry and cure treatments to impart wrinkle resistance to cotton fabric was studied by Gagliardi and Shippee, American Dyestuff Reporter 52, P300-P303 (1963). They observed small increases in fabric wrinkle resistance after relatively long periods of heating, and noted larger fabric strength losses than are obtained with formaldehyde-based crosslinking agents. These excessive strength losses and the low yield of crosslinkages were attributed to the long heat curing times needed with the inefficient catalysts then available.
A more rapid and effective curing process for introducing ester crosslinks into cotton cellulose was described by Rowland et al. Textile Research Journal 37, 933-941 (1967). Polycarboxylic acids were partially neutralized with sodium carbonate or triethylamine prior to application to the fabric in a pad, dry and heat cure type of treatment. Crosslinking of cellulose was obtained whenever the polycarboxylic acid contained three or more carboxyl groups suitably located in each molecule. With certain polycarboxylic acids, a useful level of wrinkle resistance was imparted. The conditioned wrinkle recovery angle was measured before and after five laundering cycles, and was found to decrease somewhat as a result of laundering, even though no loss of ester groups was detected. Neutralization of carboxyl groups with 2% sodium carbonate even at room temperature caused a 30% loss of ester groups. This indicates a lack of durability of the finish to alkaline solutions such as solutions of alkaline laundering detergents. The curing time needed in fabric finishing was moreover too long to permit high speed, mill-scale production.
Subsequently it was shown by Rowland and Brannan, Textile Research Journal 38. 634-643 (1968), that cotton fabrics given the above cellulose crosslinking treatment with polycarboxylic acids were recurable. Creases durable to 5 laundering cycles could be put into the fabrics by wetting the latter, folding, and applying a heated iron. Evidence was obtained that the ester crosslinkages are mobile under the influence of heat, due to a transesterification reaction taking place between ester groups and adjacent unesterified hydroxyl groups on cotton cellulose.
These findings were elaborated by Rowland et al. U.S. Pat. No. 3,526,048. Sodium carbonate or triethylamine were again the examples of bases used to partially neutralize the polycarboxylic acid subsequently applied as the cellulose crosslinking agent. Rowland et al defined their process as requiring neutralization of 1% to 50% of all carboxylic acid functionality by a .strong base. selected from the group consisting of alkali metal hydroxides, carbonates, bicarbonates, acetates, phosphates and borates, prior to impregnating the fibrous cellulose with the aqueous polycarboxylic acid and heating to induce crosslinking. A strong base selected from the group consisting of ammonia and certain amines also was indicated as suitable for the partial neutralization of the polycarboxylic acid.
Stated limitations of the process of Rowland et al are that the process cannot be conducted with acids of fewer than three carboxyl groups per molecule, or with acids containing olefinic unsaturation or hydroxyl groups. The reasons were lack of reaction with cellulose and lack of effective crosslinking of cellulose chains for development of high levels of wrinkle resistance. The limited durability of the finishes noted above was also a disadvantage, and the time required for complete curing was too long to permit practical rates of cloth finishing.